7 Alkenes Reactions and Synthesis：7的烯烃反应，合成.ppt

* Problem 7.14: Which Alkene? Polymers: * * Polymers: * * Alkene Polymers: Adding double bonds together, usually head-to-tail, forms synthetic polymers like polyethylene: * * Alkene Polymers by Radical Reactions: Initiation: * Alkene Polymers by Radical Reactions: Propagation: * Termination: Unsymmetrical alkenes (see next slide): Other “Vinyl” Polymers: * More Examples: * * Natural Rubber: Made from the sap of a number of plants, principally Hevea brasiliensis Crude rubber (latex) is Z-polyisoprene * 7.11 Biological Alkene Addition Reactions Living organisms convert organic molecules using enzymes as catalysts Many reactions are similar to organic chemistry conversions, except they occur in neutral aqueous solution at 37oC Usually very specific for reactant and stereochemistry In the Laboratory: * Prostaglandin Biosynthesis: * * Addition of H-BH2 (from BH3-THF complex) to three alkenes gives a trialkylborane Oxidation with alkaline hydrogen peroxide in water produces the alcohol derived from the alkene Hydroboration-Oxidation Forms an Alcohol from an Alkene * Orientation in Hydration via Hydroboration Regiochemistry is opposite to Markovnikov orientation OH is added to carbon with most H’s H and OH add with syn stereochemistry, to the same face of the alkene (opposite of anti addition) * Mechanism of Hydroboration Borane is a Lewis acid Alkene (p-bond) is Lewis base Transition state involves anionic development on B The components of BH3 are across C=C Hydroboration: Orientation in Addition Step * * Steric Preference Two Possible Orientations: Practice Problem 7.1 * * Practice Problem 7.2: Which alkene? * Which alkene would work best? * This one: anti-Markovnikov * Problem 7.9: Major Products? * Problem 7.10: Which Alkenes? * 7.6 Addition of Carbenes to Alkenes Carbenes are electrically neutral with six electrons in the outer shell They add symmetrically across double bonds to form cyclopropanes Formation of Dichlorocarbene * Dichlorocarbene Structure * * * Rea